Halobutanedione fungicidal compositions and method of applying the same to soil



HALOBUTANEDIONE FUNGICIDAL COMPOSI- TIONS AND METHOD OF APPLYING THE SAlVlE TO SOIL Lloyd J. Meuli, Long Beach, Calif., assignor to The Dow Chemical Company, Midland, Mich., a corporation of Delaware No Drawing. Application August 2, 1954, Serial No. 447,375

6 Claims. (Cl. 47-58) 'of crops. A further object is the provision of a practice which will include the treatment of soil and still permit the immediate utilization of the treated soil for crop purposes. Another object is the provision of a method for protecting the roots of plants against the attack of soildwelling fungi. A further object of the present invention is the provision of a novel composition adapted to be employed in the new practice for raising and protecting crops. Other objects will become apparent from the following specification and claims.

The new agronomical practice comprises treating soil United States Patent or growth media with a halobutanedione compound of the formula wherein X is chlorine or bromine and Y is hydrogenor the halogen represented by X, to benefit plants grown in the treated soil. Such practice protects the plants from the ravages of soil-dwelling fungi which attack their roots and improves crop yields as well as the emergence and growth of seedlings.

The halobutanedione compounds are non-flammable, stable, liquid materials which are somewhat soluble in many organic solvents and water and are adapted conveniently and readily to be distributed in soil or growth media. Further when so distributed, the compounds aca further advantage that the compounds permeate growth media for a short distance from the point of application depending upon the temperautre, moisture content, compactness and physical consistency of the media.

The distribution of an effective or fungicidal dosage of the compounds in soil or growth media is essential for the practice of the present invention. In general, good results are obtained when the compounds-are distributed through the growth media in the amount of from 5 to 50 parts by weight per million parts by weight of the media.

Following such treatment, the soil may be immediately seeded or otherwise employed for crop purposes, if desired. In field applications, the halobutanedione compounds may be applied to and mixed with the soil at a dosage of from about 0.4 pound to 400 pounds or more per acre, and through such a cross section of the soil as Y ionic dispersing and emulsifying agent.

2,775,057 Patented Dec. 25, 1956 ICE to provide for the presence therein of an effective concentration of the treating agent. In general field applications,

it is usually preferred that the compounds be distributed to a depth of at least two inches and at a dosage of at least 1.8 pounds per acre inchof soil. Often times it is desirable to distribute the compounds to a depth of at least 24 inches to avoid reinfestation of the soil from deepdwelling fungal organisms. In applications to the furrow seed row for the suppression of seedling disease, it is desirable that the compounds be distributed upon the. surface of the furrow at a dosage of at least 0.15 pound per acre of furrow soil surface. After such treatment, the furrow is seeded and the soil compacted about the seed according to conventional practice. In the row treatment of existing vegetation, the products may be employed with known side-dressing techniques.

In carrying out the method of the present invention, the underground parts of crops are protected against attack by soildwelling fungi by distributing in the soil or growth media the unmodified compounds. However, the present method also embraces the employment of a liquid or dust composition containing the compounds. In such usage, the compounds may be modified with one or more of a plurality of additaments or fungicide adjuvants including solvents or other liquid carriers, surface active dispersing agents and finely divided inert solids. Depending upon the concentration of the compounds, such augmented compositions are adapted to be distributed in the soil, or employed as concentrates and subsequently diluted with'additional inert carrier to produce the ultimate treating compositions. The required amount of the compounds may be supplied per acre treated in from 5 to 27,000 gallons or more of the liquid carrier or in from about 20 to 2,000 "pounds of the solid carrier.

The exact concentration of the compounds to be employed in compositions for the treatment of growth media may vary provided the required dosage of effective agent is supplied. The concentration of toxicant in liquid compositions employed to supply the desired dosage generally 'is from about 0.001 to 50 percent by weight, although as high a concentration as percent by weight may be employed. In dusts, the concentration of. the effective agent maybe from about 1 to 20 percent by weight. In compositions to be employed as concentrates, the compounds may be present in a concentration of from about 5 to percent by weight.

Liquid compositions containing the desired amount of effective agent may be prepared by dissolving the toxicant in an organic liquid such as acetone, methylene chloride, chlorobenzene, and petroleum distillates, or by dispersing the toxicant in water with or without the aid of a suitable surface active dispersing agent such as an ionic or non- The I preferred organic solvent carriers are those which are adapted to accomplish the penetration and impregnation of the soil with the toxicant compounds, and are of such volatility as to evaporate'from the growth media and leave little permanent residue therein. are'the petroleum distillates boiling almost entirely under 400'F. at atmospheric pressure and having a flash point above about 80 F.

The aqueous compositions to be employed in the present method may contain one or more water-immiscible solvents for the compounds. In such compositions, the carrier comprises an aqueous emulsion, i. e. a mixture of water-immiscible solvent, emulsifying agent and water. The choice of dispersing and emulsifying agent and the amount thereof employed is dictated by the nature of the composition type and by the ability of the agent to facilitate the dispersion of the effective agent in the aqueous carrier to produce thedesired composition; Dispersing and emulsifying agents which may be employed in Particularly desirable carriers.

3 the compositions include the condensation products of alkylene oxides with phenols and organic acids, alkyl aryl sulfonates, polyoxyethylene derivatives of sorbitan esters, complex ether alcohols, mahogany soaps-and the like.

In the preparation of dust compositions, the compounds are dispersed in and on a finely divided solid such as talc, chalk, gypsum and the like. In such operations, the finely divided carrier is mixed or wet with the toxicant or a solution thereof in a volatile organic solvent. Similarly, dust compositions containing the compounds may be prepared from various of the solidsurface active dispersing agents such as pentonite, fullers earth, attapulgite and other .clays. Depending upon the proportion of ingredients, these dust compositions may be employed as concentrates and subsequently diluted with additional solid surface active dispersing agent or with talc, chalk, gypsum and the like to obtain the desired amount of active ingredient in a composition adapted to be distributedjnsoil, Also .suchvconcentrate dust compositionsmay be dispersed in .water, with or without the aidof a dispersing-agent, to

form aqueous soil treated compositions.

A further embodiment of the presentinvention is a vnovelcomposition comprising growthmedia -or soil in admixture with an effective concentration of the compounds.

When operating in accordancewith the present invention, thesoil or growth media may be impregnated-many convenient fashion with the compounds, i. e. by simple mixing with the growth media, by applying to thesurface of soil and thereafterdragging or discing intothe ,soil to the desired depth or by employing a liquid carrier to accomplish the penetration and impregnation. In another method, the compounds are distributed upon the surface of the seed furrow and the furrow thereafter planted and compacted about the seed. In general, it is desirable that the distribution be carried out at a soil temperature of 40 F. or'higher since the effectiveness of the toxicants may be somewhat reduced at lower temperatures.

In a preferred embodiment, the method of the present invention is carried out in soil having a moisture content of from about 50 to 100 percent of the moisture equivalent of the soil. -When operating under such soil conditions, maximum controls of fungal organisms are obtained. Thompson, L. M. in Soils and Soil Fertility, McGraw-Hill Book Company, Inc. (1952) defines the moisture equivalent of a soil as equal to the percentage of water retained by wet soilafterbeing centrifuged at 1000 timesgravity. This equivalent is about the same as the so-called field capacity which may be defined as the moisture condition ofthe soil when downward movementof waterinto the soil has virtually ceased. The moisture equivalent .or field capacityis dependent primarily upon the percentage of organic matter in the soil, the size of the soil particles and the porosity of the soil.

In a further method, thedistribution may beaccomplished by introducing the toxicant in the water'employed to irrigate the soil. In this method, the amountof water may be varied inaccordance with the moisture equivalent or field capacityof the soil in order to obtain thedesired depth of distribution of the toxicant at a soil moisture contentequal to the moisture equivalent. When operating in accordance with suchmethod, toxicant distributions to a depth of from two to four feet or more may beconvenieutly o t ine The following examples illustrate -,the invention but are not to be construed as limiting the same:

Example 1 4, percent of the moisture equivalent or, field capacity of the soil. In the treating operations, the soil was placed in scalable vessels and thereafter separately injected with the acetone compositions in amount sufiicient to supply various concentrations of the butanedione compounds in the soil. After treatment, the vessels were sealed and the soil therein mechanically mixed to insure uniform distribution of the toxicant composition. After one-half hour of mixing, the soil was removed from the vessels, spread in containers to a depth of 3.5 inches and seeded to Lima beans. In a check operation, the same infested but untreated soil was similarly spread in containers and seeded with Lima beans. The containers of seeded soil were then Watered to a moisture content of about field capacity and thereafter placed in a cold room at F. and 85 percent relative humidity to provide conditions conducive to slow germination of the seed and favorable for rapid infestation of the seed with the "complex of root-rot fungi. After one week in the cold room, the containers of seeded soil were removed and thereafter maintained in a greenhouse according to conventional practices with regard to light, temperature, humidity and moisture.

During the subsequent growth period, there was observed no adverse effect upon germination and seedling growth attributable to the butanedione compounds.

Six weeks after seeding, the containers were inspected to determine the percentage emergence of seedlings and.

the plants lifted, roots washed, and. thereafter examined in order to determine the presence of disease free plants.

The results are set forth in the following table:

Concentration Concentration of Toxicant of Treating Compound in Compound in Percent Percent "Treating Compound Soil Treating Soil in Parts Seedling Disease Composition by Weight Emer- Free in Grams per per Million gence Seedlings Liter Parts by Weight of Soil l-chloro-2,3-butanedione s 10 97 92 1,4-dich1oro-2,3-butanedione 15 25 97 87 1,-bromo- 2,3-butancdlone 6 10 95 62 Checks 15 17 Example 2 Acetone solutions containing 15 grams and 3 grams of 1-bromo-2,3-butanedione were employed for the treat- ,ment of the previously described fungal infested soil. In

the treating operations, the soil was placedin scalable containers and separately injected with the acetone comditions as the treated soil.

After 3 days, the containers were opened and portions of the treated and untreated soil cultured by the dilution plate method as described by I. P. Martin in Soil Science, 69, No. 3, p. 2l532 (Marchrl950) to determine the-percent control of fungal organisms. In the latter operations, the culturingmedium employed was apeptone dextrose agar (1000 milliliters of water, 10 grams of dextrose, 5 grams of peptone, 1 gram of KH2PO4, 0.5 gram of MgSO4-7H2O and 20 grams of agar) containing 0.069 gram of rose bengal and 0.030 gram of streptomycin per liter of ultimate mixture. In the plating operations, the culturing medium was incorporated with ,about ,0.-5 .gra t n of soilsample per liter ofmediumand the, plates thereafter poured in replicatesof threeforithe cant compositions.

treated and cheek soils. The pouredplates were then incubated for3 days at 25 C. v o o After incubation, the plates were examined and counts of fungal colonies made in order to determine the percent control of the fungal organisms. The results are set forth in the following table:

Example 3 In a further operation, acetone solutions containing 15 grams of one of the toxicants, l-chloro2,3-butanedione, 1-bromo-2,3-butanedione, and l,4-dibromo-2,3-butanedione, were employed for the treatment of the same fungal infested soil. In the treating operations, the soil was placed in sealable jars and thereafter injected with the acetone solutions in an amount sufficient to supply 25 parts by weight of one of the butanedione compounds per million parts by weight of soil. Immediately after treatment, the soil in the jars was seeded'to cotton, the.

jars thereafter sealed and the seeded soil therein mechanically mixed to insure uniform distribution of the toxi- In a check operation, the same infested but untreated soil was placed in jars, the-soil seeded with cotton seeds and the jars thereafter sealed. Three days after seeding, the jars were opened, sufficient water added to each jar to encourage seedling growth and the jars immediately resealed. During the subsequent period of growth, there was observed no adverse effect upon the germination and growth of seedlings attributable to the toxicant compounds.

Ten days after seeding, the jars were opened, the seedlings removed and the roots examined in order to determine the number of disease-free plants. As a result of the examination, it was found that the seedlings from the soil which had been treated with the butanedione compounds were free of fungal disease. In contrast, all seedlings in the check soils were found to be heavily infested with the complex of root-rot fungi.

Example 4 25 parts by weight of l-chloro-2,3-butanedione, 71 parts of xylene and 4 parts of a dimeric alkylated aryl polyether alcohol (Triton X-155) are mechanically mixed together to prepare a concentrate composition in the form of an emulsifiable liquid.

Also, 95 parts by weight of 1,4-dichloro-2,3-butanedione and 5 parts of a sorbitan monolaurate polyoxyethylene derivative (Tween 20) are mechanically mixed together to prepare a dispersible liquid concentrate composition.

In a further operation, 25 parts by weight of l-bromo- 2,3-butanedione, 71 parts of fullers earth, 2 parts of an alkyl aryl sulfonate (Nacconal NR) and 2 parts of a polymerized sodium salt of a substituted benzoid aikyl sulfonic acid (Daxad No. 27) are mechanically mixed and ground together to prepare a concentrate composition in the form of a wettable powder.

These concentrates may be dispersed in water to prepare aqueous compositions which have very desirable wetting and penetrating properties. The latter aqueous compositions are adapted to be employed to treat soil and distribute the toxicant compounds therein in fungicidal concentrations.

Example 5 An emulsifiable concentrate composition comprising a toluene solution containing 24 grams of 1-chloro-2,3-butanedione, 36 grams of isopropanol and 8 grams of a polyhydricalcohol-sulfonic acid derivative (Tenlo 400) sola ni, Pythium spp. and Rhizoctonia solani.

composition containing 0.86 pound of 'l-bromo-2,3-bu

tanedione per 25 gallons of ultimate mixture was prepared from an exactly comparable concentrate composition comprising the latter butanedione material as the sole toxic ingredient. These aqueous compositions were employed for the treatment of sandy loam seed .beds heavily infested with the fungus organisms Fusarium At the time of treatment, the-soil in the seed beds had a moisture content equal to about 75 percent of the field capacity. Prior to treatment, the seed beds had been furrowed for seeding with sugar beet seed units. In the treating operations, the bottoms and sides of the furrows were sprayed with the compositions at a dosage of 25 gallons of aqueous composition per acre of furrow soil surface. Immediately following the treatments, sugar beet seed units were planted in the furrows and the soil compacted about the, seed units according, to conventional planting practices. In a check operation, similarly infested but untreated seed beds were also planted with sugar beet seed units. During the subsequent growing period therewas observed no adverse effect upon germination and growth of seedlings attributable to the toxicant compounds..

Five weeks after planting, the seed beds were examined to determine the number of seedlings emerged from each planted seed units. The results are set forth in the following table:

Example 6 The emulsifiable concentrate composition of Example 3 is dispersed in water to prepare a composition containing 100 pounds of 1-chloro-2,3-butanedione per 200 gallons of ultimate mixture. The latter composition while under agitation is metered into irrigation water at the pump outlet at the rate of 6 gallons per 1000 gallons of irrigation water. The water is in a state of turbulent flow as it comes from the pump which provides for thorough mixing of the toxicant composition therein. About 3 acre inches of the irrigation water is applied to a sandy loam soil heavily infested with F usarium solani, Pythium spp., and Rhizoctonia solani. This treatment accomplishes a wetting of the soil to a depth of about 2 feet to provide a concentration of about 28 parts by weight of 1-chloro-2,3-butanedione per million parts by weight of soil. One week following the irrigation, the soil is seeded to Lima beans. Five Weeks after seeding, the resulting stand of bean plants is examined and found to be substantially free of fungal disease.

:The expressions growth media or soil are employed in the present specification and claims in their broadest sense to be inclusive of all conventional soils, as defined in Websters New International Dictionary, Second Edition, Unabridged, published in 1937 by G. and C. Merriam Company, Springfield, Massachusetts. Thus, the terms refer to any substances or media in which vegetation may take root and grow, and are intended to include not only earth but compost, manure, muck, humus, and sand and the like, adapted to support plant growth.

I claim:

1. An agronomica-l practice which comprises impregnating'fung-us infected soil with from 5 to 50 parts by weight; of a halobutan'edione compound permillion parts :by weight of the-medium and thereafter planting-the 'treated "medium, the halobutanedlione compound being wherein X is a-member of the group consisting .of'chlorine and bromine-and Y is a member of the group consisting of hydrogen and the-halogen represented by-'X.

"2. An agrono-mioal practicewhich comprises applying to and-miXing Wit-h fungusinfected-soila fungicidal amount of a halobutanedione compound of-theformula l X-oHz.o-o.o,Hz-.Y wherein X is a member of the group consistingofchlorine and'bromineand'Y- is. amember of the group-consistinglo'f hydrogen and the halogen zrepresented by X.

3. In therpra-cticerof vagnicu-ltural:economy-the method which comprises-impregnating fungus infected soil :-with a:halobut-anedione compound of the formula wherein X is a member ofthe, group, consisting of chlorine .and'bromine and Yais a member of the group consisting of hydrogen and the halogen represented byiX,rthe impregnation being carried out to. a depth=of :at .1east 2 inches below the soil surface and at a relatively uniform dosageof from 5 toparts ,by weight of'ihefbutane dione compound per million parts by weighttof so-il.

*4. -A" concentrate composition which comprises a butanedione compound oftheformulal II x-om-w-ii-orn-Y wherein Xr-is amember of the group consisting of chlorine and bromine and Y is a memberof the group cons-isting of hydrogen and the halogen represented by X in admixture with a surfaceaactive disperi-ng agent as a fungicide adjuvant carrier.

,5. An .ag m cale pract e which comp s s impr nating fungus infected. soil with from 5 to 50 parts by weight of 1-chloro-2,3-abutanedione per million parts by weight of-th-e soil.

r '6. A-n, agronomical practice which comprises zimpreg- -nat-ing-.f-ungusinfected soil, with: from 5-=to 50 .parttsvby weight of 1-bromoe2,3rbutanedione per million. partsiby weight of :soil. 1

"ktinNoJ13113, January 26, 1925, pp. 1, 15 and 16. 

1. AN AGRONOMICAL PRACTICE WHICH COMPRISES IMPREGNATING FUNGUS INFECTED SOIL WITH FROM 5 TO 50 PARTS BY WEIGHT OF A HALOBUTANEDIONE COMPOUND PER MILLION PARTS BY WEIGHT OF THE MEDIUM AND THEREAFTER PLANTING THE TREATED MEDIUM, THE HALOBUTANEDIONE COMPOUND BEING CHARACTERIZED BY THE FORMULA 